Process of preparing diazosulphamic acids



' benzidine Patented Mar. ll, 1930 UNITED. STATES PATENT OFFICE KARI. scmmcnna AND WERNER sonmmacnna, or HOOHST-ON-THE-MA IN, enn- MANY, ASSIGNORS TO GENERAL ANILIN E WORKS, INC., OF NEW YORK, N. Y., A COB- POBATION OF DELAWARE PROCESS OF PREPARING DIAZOSULPHAMIC ACIDS No Drawing. Application filed February 17, 1927, Serial No. 169,131, and in Germany February 22, 1926.

Our present invention relates to a new process for producing diazosulphamic acids of the aromatic series.

There have already been proposed several processes for partially diazotizing polyamidated hydrocarbons of the cyclic series and derivatives thereof; but by none of these processes it is possible to carry out the said diazotization in a practical and useful way. When ortho-diamines are treated with nitrous acid azimides are obtained, whereas, meta-diamines give, besides. diazo compounds, also tetrazo compounds and bodies formed by self-coupling, and para-diamines give monodiazo compounds, sometimes besides quinones, but only in a very diflicult way and with a poor yield.

Now we have found that the monodiazo compounds in question maybe obtained in a simple manner and with a ood yield by converting the amines into s phamic acids by means of halogen-sulfonic acids or their esters in presence of a tertiary base and in such a manner that all of the amino groups contain sulfo groups, the products obtained being thereupon-treated at a low temperature with nitrous acid the quantity of which corresponds tothe amount necessary to diazotize one amino group. One sulfo group is thereby eliminated and mono-diazosulphamic acids are formed in which the other sulfo groups are relatively more firmly fixed so that they can be advantageously used, for instance by coupling them with ,B-naphthol, for the production of azo dyestuffs WhIClI are mostly soluble.

Our new process involves an important technical progress because it permits to convert for instance o-diaminobenzene into diazob'enzenesulphamic acids, m-diaminobenzene into m-diazobenzenesulphamic acid, pdiaminobenzene into p diazobenzenesulphamic acid, 1.5-diaminonaphtha1ene into 1- diazonaphthalene-5-sulphamic acid and 1.8- diaminonaphthalene into l diazo-8-naphthalenesulphamic acid, and likewise bases of the series into diazodiphenylsulphalnic acids. In the same manner may also be converted amidated azo bodies. Inthe azo dyestuffs produced for'instance from the said compounds, the sulfo groups may be split oil, for instance by heating them with an acid whereby azo dyestufl's are obtained which seem to be produced from partially diazotized diamines or polyamines. The diazosulphamicv acids may also be transformed into a great number of other compounds which otherwise can only be produced with great technical diificulties, by substituting for the diaz'o residue any other residue, for instance, by heating the aqueous solutions of the diazosulphamic acids in the presence of cuprous chloride, bromide, cyanide, or any other cuprous salt according to the Sandmeyer reaction for the substitution of diazotized amino groups.

The following examples illustrate our invention but they are not intended to limit it thereto, all parts being by weight:

1. 500 parts of dry pyridine are gradually mixed, while cooling, with 130 parts of chlorosulfonic acid and into this mixture are introduced at about 2530 C. 54 parts of paraphenylenediamine whereupon the whole is heated for about 2 hours to about 607 0 C. The mass is allowed to cool and is introduced into a solution of 200 parts of sodiuin I carbonate in 500 parts of water; the pyridine preparation of the p-diazobenzenesulphamic acid and the solution may directly be further treated. The solution is cooled with ice, rendered just acid; 120 parts ofhydrochloric acid of 20 B. are then added thereto whereupon a solution of about 35 parts of sodium nitrite, according to requirement, are run into the mass at 05' C. until the absorption of the nitrous acid has almost ceased. The

following equation SOzNa The diazo compound thus obtained is also so readily soluble that it cannot be isolated.

- By coupling it with, for instance, ,B-naphthol,

a red water-soluble dyestufi is obtained.

2. By replacing the para-phenylenediamine, used in Example 1, by 61 parts of m-toluylenediamine-12-4 and carrying out the further operations as indicated in Example 1, the disulphamic acid of 2.4-toluylenediamine is obtained and from the latter the mono-diazo compound of toluylmonosulphamic acid, which contains the diazo group presumably in i position and, when coupled with B-naphthol for instance, yields a red water-soluble azo dyestufi. The reaction so probably occurs according to the following equation:

CH; NH.SO;Na NH-SO:

111101 1 mol NaNOz N SO|Na f ii Nnsoma 1 1 mol NBNO:

do: NH.SOaNa NH l. In exactly the same manner the corresponding 4.4-diphenyldisulphamic acid is obtained from 92 parts of benzidine, which acid is considerably more diflicultly soluble and the sodium salt of which crystallizes NH 1 m0] NaNO:

from the solution on cooling. Analysis shows that the product is a disulphamic acid. This disulphamic acid when treated, as indicated in Example 1, with nitrous acid in the cold, yields a diazodiphenylsulphamic acid which partly precipitates and which, when coupled for instance with B-naphthol gives a reddishviolet dyestuif. The reaction probably occurs according to the following equation:

5. By treating 7 9 parts of 1.5-naphthylenediamine in the same manner as indicated in Example 1, a 1.5-naphthalenedisulphamic acid is formed, the salt of which crystallizes from water and, when treated with nitrous I acid, forms a yellow soluble l-diazonaphthalene-5-sulphamic acid which, when coupled with, for instance, ,B-naphthol, yields a red, soluble dyestuff. The reaction probably occurs according to the following equation:

N OS-NH Nn-so Na 8 H111 NEN We claim:

1. The process for preparing diazosulphamic acids of the aromatic series, which con sists in converting an aromatic diamine by means of an agent capable of splitting oil SO ,-into the disulphamic acid and treating the latter with nitrous acid, the quantity of which corresponds to the amount necessary to diazotize one amino group.

2. The process of preparing diazoarylsulphamic acids, which consists in treating an arylenedisulphaniic acid with nitrous acid, the quantity of which corresponds to the amount necessary to diazotize one amino group.

3. The process of preparing diazoarylsulphamic acids of the enzene series, which consists in treating a, disulphamic acid of the benzene series nitrous acid, the quantity of which corresponds to the amount necessary to diazotize one amino group.

4. The process for preparing diazotolylsulphamic acids, which consists in treating a toluylenedisulphamic acid with nitrous acid,

the quantity of which corresponds to the amount necessary to diazotize one ammo group.

In testimony whereof, we aflix our signatures,

KARL SGHIRMACHER.

I WERNER SOHIRMACHER. 

